TWI416599B - Liquid deposition method - Google Patents

Abstract

The liquid phase deposition method of the present invention is to form a mask pattern on the surface of the substrate, in which a growth region of silicon dioxide is defined by the mask pattern. Then utilizes the liquid phase deposition method to grow the silicon dioxide, and finally removes the mask pattern for forming a silicon dioxide film on the substrate so as to complete a patterned substrate.

Description

Liquid deposition method

The present invention relates to a liquid deposition method, and more particularly to a liquid deposition method capable of forming a patterned elongated substrate.

According to the application of the light-emitting diode, it has become more and more popular, from the early indication to the now widely used in the display field, because the light-emitting diode has the characteristics of high efficiency, good light quality, power saving and long life. Therefore, there are more and more downstream applications including flat panel displays, portable displays, lighting and infrared light emitting diodes.

In addition, in many light-emitting diode luminescent materials, the matching substrate lattice (SL) structure is usually used by adjusting the ratio of binary, ternary, or quaternary materials, and then using different atomic ratios of different sizes. In order to adjust the size of the energy gap of the semiconductor, the light-emitting diode has a suitable wavelength of light emission; however, since the adjustment is performed in a matching manner, the epitaxial parameters are more complicated. Therefore, if a high-quality light-emitting diode element is to be obtained, the selection of the substrate becomes a relatively basic and important one.

The main function of the foregoing substrate is for carrying and epitaxy, and its quality directly affects various characteristics after forming the LED component, including: brightness, luminous efficiency and service life, such as: substrate and The degree of lattice matching between the epitaxial materials will directly affect the number of internal defects of the light-emitting diode elements, further affecting the luminous efficiency and service life of the light-emitting diode elements. Therefore, having a suitable substrate can be said to be an important element for forming a high-quality light-emitting diode light-emitting element, wherein the substrate surface patterning has been regarded as One of the effective methods for reducing the internal defects of the light-emitting diode element and reducing the differential discharge density and thereby improving the luminous efficiency of the light-emitting diode.

There are currently known ways to form a pattern: deposition or etching removal. For example, as disclosed in Taiwan Patent Publication No. 297916, the patent name "Oxide Layer Deposition Method", Taiwan Patent Publication No. 366526, the patent name "a Liquid Phase Cerium Oxide Film (LPD-SiO2) Mass Production Deposition Technology" Taiwan Patent Publication No. 492080, the patent name "a composition for the deposition of cerium oxide in a liquid phase on a tungsten carbide and a tantalum nitride", is deposited by a liquid deposition method on a surface of a substrate.

Furthermore, as disclosed in Taiwan Patent Publication No. 388073, the patent name "a liquid deposition method for growing titanium dioxide on a gallium arsenide substrate" and Taiwan Patent Publication No. I247392, the patent name "Use on Indium Phosphide Wafers" A method for producing a titanium dioxide thin film by liquid deposition, etc., is a method in which a titanium oxide film is deposited on a surface of a substrate by a liquid deposition method.

In addition, Hirotsugu Nagayama, et al., 1988 [A New Process for Silica Coating] (J. Electrochem. Soc., Volume 135, Issue 8, pp. 2013-2016), proposed a method by liquid deposition. A ruthenium dioxide film is deposited on the surface of the glass; however, the above-described liquid deposition method is used to form a pattern on the surface of the substrate in a random manner, and cannot be patterned according to a specific region required.

In addition, the etching removal method is as described in Taiwan Patent Publication No. I321856, the patent name "Manufacturing Method of Nano Pattern and Its Application to Light-Emitting Elements", in which a metal layer is first formed on the surface of the substrate. A superalloy treatment is further performed to cause the metal layer to form a plurality of nano metal particles on the first portion of the surface of the substrate and expose the second portion of the surface of the substrate. Next, form a mediation The electrical layer is on the second portion of the surface of the substrate, and the nano metal particles are removed to expose the first portion of the surface of the substrate. Next, the dielectric layer is used as a mask to remove the first portion exposed on the surface of the substrate, and a nano pattern is formed on the surface of the substrate. Then, the dielectric layer is removed; the manufacturing method can form a nano pattern on the surface of the substrate, but the above process is complicated, and the manufacturing cost is relatively increased, the desire of the manufacturer to develop is reduced, and the economic benefit is also detracted.

In view of the above, the present invention provides a liquid deposition method capable of forming a liquid phase deposition method of a patterned substrate, which is the main object thereof.

In order to achieve the above object, the liquid deposition method of the present invention mainly forms a photoresist mask pattern on the surface of the crystal growth substrate, and the photoresist mask pattern defines a region where the germanium dioxide is to be grown, and the liquid phase is reused. The germanium dioxide is grown by a deposition method, and finally the photoresist mask pattern is removed, and a patterned ceria film is formed on the surface of the crystal growth substrate to form a patterned crystal growth substrate.

The liquid deposition method of the present invention can be applied to a long crystal substrate, such that a surface of the crystal growth substrate is formed with a hafnium oxide film or an irregular pattern to form a patterned substrate, which facilitates subsequent processing of the substrate surface, for example, Performing an epitaxial process to form a light-emitting element can reduce defects caused by epitaxy, improve the yield of subsequent components, and increase the light extraction rate.

The features of the present invention can be clearly understood by referring to the drawings and the detailed description of the embodiments.

The present invention mainly provides a liquid deposition method, as shown in the second figure, which comprises at least the following steps: Step A, determining a region on the surface of the substrate to grow germanium dioxide, forming a mask pattern on the surface of the substrate, The mask pattern defines a region in which the cerium oxide is to be grown. As shown in the embodiment of FIG. 3A, the surface of the substrate 70 may be covered with a photoresist layer 72, and the photoresist is formed by a yellow light process. The layer 72 is formed with a plurality of holes 73, as shown in the third figure (B), as a mask pattern, or the photoresist layer may be formed with a plurality of holes by a nano transfer technique to serve as a mask. a pattern, or a metal aluminum layer may be coated on the surface of the substrate, and the metal aluminum layer is oxidized into a plurality of pore structures through an anodizing treatment step as a mask pattern; and step B is performed by using a liquid deposition method on the surface of the substrate. Growing ceria; step C, performing mask pattern removal, removing the mask pattern, forming a patterned ceria film 71 on the surface of the substrate 70, as shown in the third figure (C), to form a patterned substrate; The mask map To determine the pattern of the shaped cerium oxide, as shown in the figure, the pattern of the plurality of cerium oxides 74 arranged in a regular array, or, as shown in the fourth figure, may be a film or an irregular arrangement. The pattern, of course, can also form a nano pattern.

As shown in the fifth figure, the liquid deposition method in the step B is: (i) placing hydrofluoric acid (H ₂ SiF ₆ ) and silicone into the first accommodating groove 10, the first accommodating A stirrer 11 is disposed in the tank 10 to uniformly mix the hydrofluoric acid and the silicone into the first mixed liquid 61, and provides a filter pump 30. The filter pump 30 is provided with a water inlet 31 and a water outlet 32. The water inlet 31 penetrates into the first accommodating groove 10, and the water outlet 32 penetrates into the second accommodating groove 20 to filter the first mixed liquid 61 from the first accommodating groove 10 and transfer it to the second. (ii) adding boric acid to the second accommodating tank 20 by using a line 40, uniformly mixing the boric acid with the first mixed liquid to form a second mixed liquid, and the second accommodating tank 20 A stirrer 21 is disposed to uniformly mix the first mixed liquid 61 with boric acid to form a second mixed liquid 62. The second mixed liquid 62 contains saturated cerium oxide, and the second accommodating tank 20 is surrounded and heated. The second mixed liquid 62 in the second accommodating tank 20 is heated; and the first mixed liquid reacts with boric acid to form a second mixed liquid, and the chemical reaction equation is as follows :

(iii) placing the substrate in the second mixture to deposit cerium oxide in a region of the substrate not covered by the mask pattern.

As shown in the embodiment of the sixth embodiment, the substrate 70 can be immersed in the second accommodating groove 20 by a fixing component 80 for fixing at least one substrate 70. The substrate 70 can be sapphire. And zinc oxide, gallium nitride, tantalum carbide, quartz, tantalum, lithium aluminate or spinel material, and the substrate 70 is immersed in the second accommodating space 21 to be in contact with the second mixed liquid 63, the fixing component 80 The base 81 and the mechanical arm 83 are provided. The bottom frame 811 is provided with a through hole 812 opposite to the pedestal 82, and the mechanical arm 83 is connected to the pedestal 81, and the pedestal 81 is controlled to be immersed in the second accommodating space 21 to make the second The mixed liquid 63 can be in contact with the substrate 70 provided on each of the cymbals 82 through the through holes 812, and the effect of depositing the cerium oxide contained in the second mixed liquid 63 on the surface of the substrate 70 can be achieved.

In the liquid deposition method of each of the above embodiments, by controlling different temperatures Degree, addition of boric acid addition amount and pH value, etc., can control the growth of liquid phase deposition of cerium oxide, wherein the heating temperature is preferably 45-55 ° C, and the boric acid is preferably added in an amount of 5-30 ml. The pH of the second mixed liquid is preferably 6-7, and the preferred control parameters can form a preferred cerium oxide deposition type; the substrate prepared by the liquid deposition method of the present invention has a ruthenium dioxide film on the surface or not The pattern of the specification arrangement or the array of cerium oxide helps the surface to be subjected to subsequent processes, such as performing an epitaxial process, which can reduce defects caused by epitaxy, improve the yield of subsequent components, and improve light. Extraction rate.

Furthermore, the steps of the above embodiments may be further performed by an etching process (which may be dry etching or wet etching) to form another patterned substrate, and another patterned substrate may be patterned to pattern the cerium oxide film or The pattern is removed or retained without specification, and the light-emitting element can be further formed by an epitaxial process.

It is worth mentioning that the present invention provides a manufacturing method which is relatively simple in process, and the present invention can quickly achieve the purpose of selectively depositing patterned nanostructures compared to conventional manufacturing methods.

As described above, the present invention provides a preferred and feasible liquid deposition method, and the invention patent application is provided according to the law; the technical content and technical features of the present invention are disclosed above, but those skilled in the art may still be based on the present invention. The disclosure is made without departing from the spirit and scope of the invention. Therefore, the scope of the present invention should be construed as being limited by the scope of the appended claims

100‧‧‧Lighting diode structure

32‧‧‧Water outlet

110‧‧‧Substrate

61‧‧‧First Mixture

120‧‧‧First semiconductor layer

62‧‧‧Second mixture

122‧‧‧ electrodes

70‧‧‧Substrate

130‧‧‧Lighting layer

71‧‧‧2O2 film

140‧‧‧Second semiconductor layer

72‧‧‧Photoresist layer

150‧‧‧ohm contact layer

73‧‧‧ hole-like structure

142‧‧‧electrode

74‧‧‧2 cerium oxide

10‧‧‧First accommodating slot

80‧‧‧Fixed components

11‧‧‧Agitator

81‧‧‧ bearing seat

20‧‧‧Second accommodating slot

811‧‧‧ bottom frame

21‧‧‧Agitator

812‧‧‧Perforation

40‧‧‧pipe

82‧‧‧匣座

30‧‧‧Filter pump

31‧‧‧ water inlet

83‧‧‧ Robotic arm

The first figure is a schematic cross-sectional view of a conventional light-emitting diode structure.

The second figure is a schematic flow chart of the liquid phase deposition method in the present invention.

The third figures (A) to (C) are schematic views showing the implementation of the mask pattern in the present invention.

The fourth figure is a schematic structural view of the patterned substrate in the present invention.

The fifth drawing is a perspective view of the structure in which the substrate is subjected to liquid deposition in the present invention.

The sixth figure is a schematic view showing the structure of the liquid phase deposition of the substrate in the present invention.

The seventh drawing is a perspective view of the structure of the fixing assembly of the present invention.

Claims (14)

A liquid deposition method comprising at least the steps of: providing a long crystal substrate; determining a region of the surface of the crystal substrate on which the germanium dioxide is to be grown, forming a photoresist mask pattern on the surface of the crystal substrate The photoresist mask pattern defines a region in which the germanium oxide is to be grown, wherein the photoresist mask pattern is formed with a plurality of pore structures; the germanium dioxide is grown on the surface of the crystal substrate by liquid deposition; and the photoresist is formed. The mask pattern is removed, and the photoresist mask pattern is removed to form a patterned ceria film on the surface of the crystal substrate. The liquid deposition method according to claim 1, wherein the step of determining a region to grow germanium oxide is performed by coating a surface of the substrate with a photoresist layer, and forming the photoresist layer by a nano transfer technique. A hole-like structure to serve as a mask pattern. The liquid deposition method according to claim 1, wherein the growing cerium oxide step comprises: (i) uniformly mixing the fluorinated acid and the cerium into the first mixed liquid, and (ii) adding the boric acid to the first mixing; The liquid is uniformly mixed into a second mixed liquid; and (iii) the long crystal substrate is placed in the second mixed liquid to deposit cerium oxide in a region of the substrate not covered by the mask pattern. The method of claim 3, wherein the hydrofluoric acid and the silicone are placed in a first receiving tank, and the first receiving tank is provided with a stirrer to uniformly homogenize the hydrofluoric acid and the silicone. Mixing into a first mixed liquid, and providing a filter pump to filter and transfer the first mixed liquid to a second accommodating tank, and boric acid is added to a second accommodating tank, the second accommodating tank A stirrer is provided to uniformly mix the first mixture with boric acid to form a second mixture. The liquid deposition method of claim 4, wherein the second accommodating tank is surrounded by a heater, and the second mixed liquid in the second accommodating tank is heated at a temperature of 45 to 55 ° C. It is better. The liquid deposition method of claim 4, wherein the filter pump is provided with a water inlet and a water outlet, the water inlet is deep in the first receiving groove, and the water outlet is deep in the second receiving Inside the slot. The liquid deposition method according to claim 4, wherein the crystal growth substrate is immersed in the second accommodating groove by a fixing member. The liquid deposition method of claim 7, wherein the fixing component is provided with a carrier, at least one cymbal holder and a mechanical arm, each pedestal is disposed on the carrier and configured to receive the substrate, and the bearing The base is provided with a bottom frame, and each of the seats is disposed on the bottom frame, and the bottom frame is provided with perforations relative to the respective seats. The liquid deposition method according to claim 3, wherein the boric acid is preferably added in an amount of 5 to 30 ml. The liquid deposition method according to claim 3, wherein the pH of the second mixed liquid is preferably 6-7. The liquid deposition method according to any one of claims 1 to 10, wherein the crystal growth substrate is sapphire, zinc oxide, gallium nitride, tantalum carbide, quartz, hafnium, lithium aluminate or spinel. The liquid deposition method according to any one of claims 1 to 10, wherein the substrate having the patterned hafnium oxide film can be further formed into another patterned substrate by an etching process. The liquid deposition method of claim 12, wherein the etching process comprises at least dry etching or wet etching. The liquid deposition method of claim 12, wherein the another patterned substrate can remove or retain the patterned ceria film on the surface.